KR20180048453A - Laminated optical film, method for producing laminated optical film, optical member, and image display device - Google Patents

Abstract

An object of the present invention is to provide a laminated optical film capable of achieving both a high porosity (porosity) and excellent scratch resistance. In the laminated optical film of the present invention, a void layer is formed on a resin film, and a cover layer is directly formed on the void layer. The void layer has a contact angle of water of 90 ° or more and a porosity of 30 volume %.

Description

TECHNICAL FIELD [0001] The present invention relates to a laminated optical film, a laminated optical film, a method of manufacturing a laminated optical film, an optical member, and an image display apparatus.

The present invention relates to a laminated optical film, a method for producing a laminated optical film, an optical member, and an image display apparatus.

When the two substrates are arranged at regular intervals, the air gap between both substrates becomes an air layer. Thus, the air layer formed between the substrates functions as a low refractive layer that totally reflects light, for example. For this reason, for example, in the case of an optical film, members such as a prism, a polarizing film, and a polarizing plate are disposed at a certain distance to form an air layer which becomes a low refractive index layer between the members. However, in order to form the air layer as described above, since the members must be arranged at a certain distance, the members can not be laminated in order, and it takes time to manufacture them. In addition, when optical members are combined through a spacer (frame) or the like in order to hold the air layer, the total thickness becomes large, which is against the demand for thinness and weight reduction.

In order to solve such a problem, an attempt has been made to apply a void layer exhibiting low refractive index instead of an air layer formed by voids between members (see, for example, Non-Patent Document 1).

 J. Mater. Chem., 2011, 21, 14830-14837

In the development of the above member, it is necessary to design the void ratio to be high in order to exhibit low refractive index. However, if the porosity is increased, the bulk density of the member is lowered, so that the strength is significantly lowered and the scratch resistance is lowered. Also in Non-Patent Document 1, there is a problem that the obtained air gap layer is inferior in film strength and scratch resistance is low. Thus, the development of a laminated optical film that combines high porosity (porosity) and excellent scratch resistance has not been reported.

Therefore, an object of the present invention is to provide a laminated optical film, a method for producing a laminated optical film, an optical member, and an image display apparatus which can achieve both a high porosity (porosity) and excellent scratch resistance.

In order to achieve the above object, in the laminated optical film of the present invention,

A void layer is formed on the resin film,

Further, a cover layer is formed directly on the void layer,

The void layer has a contact angle of water of 90 DEG or more and a porosity of 30% by volume or more.

In the method for producing a laminated optical film of the present invention,

As a method for producing the above laminated optical film of the present invention,

A void layer forming step of forming the void layer on the resin film, and

And the cover layer forming step of directly forming the cover layer on the gap layer.

The optical member of the present invention includes the above-described laminated optical film of the present invention.

The image display apparatus of the present invention includes the optical member of the present invention.

The laminated optical film of the present invention can achieve both a high porosity (porosity) and excellent scratch resistance. Further, according to the method for producing a laminated optical film of the present invention, it is possible to produce the laminated optical film of the present invention having both high porosity (porosity) and excellent scratch resistance. The laminated optical film of the present invention can be used, for example, in the optical member and the image display apparatus of the present invention, but the present invention is not limited thereto and may be used for any purpose.

1 is a process sectional view schematically showing an example of a method of forming an air gap layer and a cover layer on a resin film in the present invention.
Fig. 2 schematically shows a part of the process in the production method of the laminated optical film of the invention (hereinafter also referred to as " the laminated optical film roll of the present invention " FIG.
Fig. 3 is a diagram schematically showing a part of the process in the production method of the laminated optical film roll of the invention and another example of the device used in the process.

In the laminated optical film of the present invention, for example, the porosity of the cover layer is 10% by volume or less.

In the laminated optical film of the present invention or the method of producing the laminated optical film of the present invention, the cover layer may be a layer formed by coating with, for example, an aqueous coating material. Further, the cover layer may be, for example, a layer having scratch resistance.

In the laminated optical film of the present invention, the cover layer includes at least one of, for example, a water-soluble crosslinking agent and a water-soluble polymer.

In the laminated optical film of the present invention or the production method of the laminated optical film of the present invention, the cover layer may be formed by, for example, coating the raw material of the cover layer raw material liquid directly on the above- Or may be formed by applying a film on another substrate and then transferring the film. Further, after the cover layer is laminated on the void layer, at least one of heating and light irradiation may be performed. The cover layer raw material liquid may be, for example, a liquid containing a compound capable of decomposing by heating or light irradiation to generate a base. For example, a liquid containing at least one of a monomer and an oligomer of a water-soluble alkoxysilane And a crosslinked product formed from at least one of the monomer and the oligomer of the water-soluble alkoxysilane.

In the laminated optical film of the present invention, the void layer and the cover layer may include, for example, a crosslinked body formed from a monomer and / or oligomer of water-soluble alkoxysilane or a monomer and / or oligomer of water-soluble alkoxysilane.

In the laminated optical film of the present invention, the void layer may be a layer formed of a porous material including fine pore particles and / or a layer formed of a fibrous material such as nanofibers.

In the laminated optical film of the present invention, the refractive index of the void layer is, for example, 1.3 or less.

In the method for producing a laminated optical film of the present invention, the cover layer forming step may be carried out, for example, by forming a cover layer material solution coating layer directly coating the cover layer raw material liquid containing the material of the cover layer on the gap layer And a transfer step of transferring the cover layer produced by coating the raw material liquid of the cover layer on the process or other substrate onto the void layer. The cover layer raw material solution may be dried, for example, in the step of coating the raw material solution of the cover layer directly on the void layer or on another substrate. The drying may be performed, for example, by heating. After the cover layer raw material solution coating process or the transfer process, the cover layer is formed by at least one of, for example, additional heating and light irradiation. The liquid for the cover layer raw material may be, for example, a liquid containing a compound capable of decomposing by heating or light irradiation to generate a base. After the cover layer raw material liquid drying step, for example, the cover layer may be further formed by heating at 80 DEG C or lower for 1 hour or more.

In the method for producing a laminated optical film of the present invention, the liquid for the cover layer raw material is, for example, a liquid containing at least one of a monomer and an oligomer of a water-soluble alkoxysilane.

In the method for producing a laminated optical film of the present invention, for example, the pore layer is a porous article chemically bonded to the pore particles, and in the pore layer forming step, for example, Are chemically bonded. In the present invention, the shape of the " particle " (for example, the fine pore particle or the like) is not particularly limited and may be, for example, spherical or other shapes. In the present invention, the fine pore particle may be, for example, a sol-gel salt pillar-shaped particle, a nanoparticle (hollow nanosilica / nano-balloon particle) or the like. In the method for producing a laminated optical film of the present invention, the fine pore particle is, for example, a fine pore particle of a silicon compound, and the porous article is a silicon porous article. The fine pore particles of the silicon compound include, for example, a pulverized product of a gelated silica compound. As another form of the void layer, there is a void layer formed of a fibrous material such as nanofibers, and the fibrous material is entangled to form a layer including voids. The method for producing such a void layer is not particularly limited, but is, for example, the same as the void layer of a porous article in which the fine pore particles are chemically bonded to each other. Also included are void layers formed using hollow nanoparticles or nano-clays, and void layers formed using hollow nano-balloons or magnesium fluoride. The void layer may be a void layer made of a single constituent material or a void layer made of a plurality of constituent materials. The shape of the void layer may be a single shape or a plurality of voids of the above-described shape. Hereinafter, the porous layer of the porous material in which the fine pore particles are chemically bonded to each other will be mainly described.

In the method for producing a laminated optical film of the present invention, the porous structure of the porous article is, for example, a soft structure having a continuous hole structure.

In the method for producing a laminated optical film of the present invention, for example, a method of producing a liquid containing the fine pore particles, a step of producing a containing liquid, a coating step of coating the liquid containing the resin, The porous layer is formed by, for example, chemically bonding the fine pore particles in the void layer forming step. In the void layer forming step, for example, the microporous particles are chemically bonded to each other by the action of a catalyst to form the void layer. The catalyst is, for example, a basic catalyst, and the containing liquid includes, for example, a base generator that generates the basic catalyst by light or heat. In the void layer forming step, for example, the microporous particles are chemically bonded to each other by light irradiation to form the void layer. In the void layer forming step, for example, by heating, the microporous particles are chemically bonded to each other to form the void layer.

Hereinafter, the present invention will be described in more detail by way of example. However, the present invention is not limited and limited by the following description.

As described above, in the laminated optical film of the present invention, the void layer is formed on the resin film and the cover layer is directly formed on the void layer. The void layer has a contact angle of water of 90 ° or more, , And a porosity of 30% by volume or more.

As described above, the laminated optical film of the present invention can achieve both high porosity (porosity) and excellent scratch resistance. This mechanism (mechanism) is unknown, but is assumed, for example, by the following description. First, by directly forming the cover layer on the gap layer, the scratch resistance of the gap layer is improved. The gap layer has a water contact angle of 90 DEG or more, and has a very high water repellency. Therefore, even if a cover layer is formed directly on the gap layer, the material for forming the cover layer can suppress the void structure of the gap layer due to the water repellent effect of the gap layer. Further, the porosity of the void layer is not less than 30% by volume and has a high porosity. Thus, it is presumed that the laminated optical film of the present invention can have both a high porosity and excellent abrasion resistance. However, this reason (mechanism) is an example of an assumed reason (mechanism), and does not limit the present invention.

Hereinafter, the laminated optical film of the present invention, which is not in the form of a roll, and the laminated optical film of the invention (the above-mentioned "laminated optical film roll of the present invention") in the form of a roll are collectively referred to simply as "laminated optical film of the present invention" . That is, in the following, the term "laminated optical film of the present invention" includes the laminated optical film roll of the present invention unless otherwise specified. Further, the laminated optical film of the present invention which is not in a roll form can be obtained by, for example, cutting out a part of the laminated optical film roll of the present invention.

[One. Laminated optical film]

The laminated optical film of the present invention can be produced, for example, by forming the above-mentioned void layer, the cover layer and the resin film, and the above-mentioned void layer is laminated on the above resin film, do. The laminated optical film may be a low refractive material characterized by having the above characteristics.

[Resin film]

In the laminated optical film of the present invention, the resin film is not particularly limited, and examples of the resin include polyethylene terephthalate (PET), acrylic, cellulose acetate propionate (CAP), cycloolefin polymer Thermoplastic resins having excellent transparency such as polypropylene (COP), triacetylcellulose (TAC), polyethylene naphthalate (PEN), polyethylene (PE), polypropylene (PP) and polycarbonate (PC).

The void layer (hereinafter referred to as " void layer of the present invention ") in the laminated optical film of the present invention may be directly laminated on the resin film, or may be laminated via another layer.

[Void layer]

The void layer of the present invention is characterized in that the lower limit of the contact angle of water is 90 ° or more, for example 95 ° or more, for example 100 ° or more, the upper limit of the contact angle of water is, For example, not more than 145 deg., For example not more than 140 deg. And the range is, for example, not less than 90 deg. And not more than 150 deg., For example not less than 95 deg. And not more than 145 deg. ° or more and 140 ° or less. The contact angle is a value measured using, for example, " fully automatic contact angle meter DM700 " manufactured by Kyowa Interface Science Co., Ltd.

The upper limit of porosity is, for example, not more than 80% by volume, the lower limit of the porosity is, for example, not less than 30% by volume, not less than 40% by volume, not less than 45% For example, not less than 70 vol% and not more than 65 vol%, and the range is, for example, not less than 30 vol% and not more than 80 vol%, for example, not less than 40 vol% and not more than 80 vol% Or more and 70 vol% or less, for example, 50 vol% or more and 65 vol% or less. The porosity can be measured by the following method based on the film density of the void layer.

(Evaluation of film density, porosity)

After forming a void layer (void layer of the present invention) on a substrate (acrylic film), an X-ray diffraction device (RINT-2000 manufactured by RIGAKU Co., Ltd.) The X-ray reflectance of the region is measured. Then, after the fitting of Intensity and 2?, The film density (g / cm 3) is calculated from the total reflection critical angle of the laminate (void layer / base material) and the porosity (P%) is calculated by the following equation .

Porosity (P%) = 45.48 占 Film density (g / cm3) + 100 (%)

The void layer of the present invention has, for example, a hole structure. The pore size of the hole indicates the diameter of the major axis among the diameter of the major axis of the pore (hole) and the minor axis diameter. A preferred pore size is, for example, from 2 nm to 500 nm. The pore size is set such that the lower limit thereof is, for example, 2 nm or more, 5 nm or more, 10 nm or more and 20 nm or more and the upper limit thereof is, for example, 500 nm or less, 200 nm or less and 100 nm or less , And the range is, for example, 2 nm to 500 nm, 5 nm to 500 nm, 10 nm to 200 nm, and 20 nm to 100 nm. Since the desired pore size is determined depending on the use of the pore structure, it is necessary to adjust the pore size to a desired pore size, for example, according to the purpose. The pore size can be evaluated, for example, by the following method.

(Evaluation of pore size)

In the present invention, the pore size can be quantified by the BET test method. Specifically, 0.1 g of the sample (the void layer of the present invention) was put into a capillary of a specific surface area measuring apparatus (ASEM2020, manufactured by Micromeritics Co., Ltd.), followed by vacuum drying at room temperature for 24 hours, Degassing gas. Then, the adsorption isotherm is drawn by adsorbing nitrogen gas to the sample to obtain the pore distribution. Thereby, the pore size can be evaluated.

In the void layer of the present invention, haze indicating transparency is not particularly limited, and its upper limit is, for example, less than 5% and less than 3%. The lower limit is, for example, 0.1% or more and 0.2% or more, and the range is, for example, 0.1% or more and less than 5% or less than 0.2% or less and 3% or less.

The haze can be measured, for example, by the following method.

(Evaluation of Hayes)

The void layer (void layer of the present invention) was cut into a size of 50 mm x 50 mm and set on a haze meter (HM-150 manufactured by Murakami Color Research Laboratory) to measure haze. With respect to the haze value, the calculation is performed by the following expression.

Haze (%) = [diffuse transmittance (%) / total light transmittance (%)] x 100 (%

The refractive index is generally referred to as the refractive index of the medium, the ratio of the propagation speed of the wavefront of light in vacuum to the propagation velocity in the medium. The refractive index of the void layer of the present invention is such that the upper limit thereof is, for example, 1.3 or less, 1.25 or less, 1.2 or less and 1.15 or less and the lower limit thereof is 1.05 or more, 1.06 or more, 1.07 or more, For example, 1.05 or more to 1.3 or less, 1.06 or more to 1.25 or less, or 1.07 or more to 1.2 or less.

In the present invention, the refractive index refers to a refractive index measured at a wavelength of 550 nm unless otherwise stated. The method of measuring the refractive index is not particularly limited, and can be measured by the following method, for example.

(Evaluation of Refractive Index)

After forming the void layer (void layer of the present invention) on the acrylic film, it is cut into a size of 50 mm x 50 mm, and this is applied to the surface of the glass plate (thickness: 3 mm) with the cover layer. The center portion of the rear surface of the glass plate (about 20 mm in diameter) is painted with black magic to prepare a sample that does not reflect on the back surface of the glass plate. The sample is set in an ellipsometer (VASE, manufactured by J. A. Woollam Japan), and the refractive index is measured under the conditions of a wavelength of 500 nm and an incident angle of 50 to 80 degrees, and the average value is taken as a refractive index.

The thickness of the void layer of the present invention is not particularly limited and the lower limit may be 0.01 탆 or more, 0.05 탆 or more, 0.1 탆 or more and 0.3 탆 or more and the upper limit may be 1000 탆 or less , 100 μm or less, 80 μm or less, 50 μm or less, 10 μm or less, and the range is, for example, 0.01 to 100 μm.

In the laminated optical film of the present invention, the void layer may contain, for example, a portion directly or indirectly chemically bonded to one or a plurality of kinds of constituent units forming a fine void structure. Further, for example, in the void layer, even if the constitutional units are in contact with each other, there may exist a portion which is not chemically bonded. Further, in the present invention, "indirectly bonding" between the constitutional units indicates that the constitutional units are bound to each other by intermediating a small amount of the binder component in an amount not more than the constitutional unit amount. The term " directly bonded " between the constituent units means that the constituent units are directly bonded without interposing the binder component or the like. The bonding of the structural units may be, for example, a bonding via a catalytic action. The bonding between the structural units may include, for example, a hydrogen bond or a covalent bond. In the present invention, the constituent unit for forming the void layer may be composed of, for example, a structure having at least one shape of a particulate shape, a fibrous shape, or a flat plate shape. The particulate and flat constituent units may be made of, for example, an inorganic material. The constituent elements of the particulate constituent unit may include at least one element selected from the group consisting of Si, Mg, Al, Ti, Zn, and Zr, for example. The structure (constitutional unit) for forming the particle phase may be either an actual particle or a hollow particle. Specific examples thereof include silicone particles, silicon particles having micropores, silica hollow nanoparticles, and silica hollow nanoparticles. The constituent unit of the fibrous phase is, for example, nanofiber having a diameter of nano-size, and specifically cellulose nano fiber, alumina nanofiber and the like can be mentioned. The planar structural unit may be, for example, a nano-clay, and specifically a nano-sized bentonite (for example, Kunipia F [trade name]). The fibrous constitutional unit is not particularly limited and includes, for example, carbon nanofibers, cellulose nanofibers, alumina nanofibers, chitin nanofibers, chitosan nanofibers, polymer nanofibers, glass nanofibers, and silica nanofibers. At least one fibrous material selected from the group consisting of The constituent unit may be, for example, fine pore particles. For example, the void layer is a porous article chemically bonded to the microporous particles. In the void layer forming step, for example, the microporous particles may be chemically bonded directly or indirectly with each other. In this case, as mentioned above, for example, a small amount of the binder component may be indirectly bonded to each other via a binder of not more than the amount of the fine pore particles. In the present invention, the shape of the " particle " (for example, the fine pore particle or the like) is not particularly limited and may be, for example, spherical or other shapes. In the present invention, the fine pore particle may be, for example, a sol-gel salt pillar-shaped particle, a nanoparticle (hollow nanosilica / nano-balloon particle), or a nanofiber, as described above. In the method for producing a laminated film of the present invention, the microporous particles are, for example, microporous particles of a silicon compound, and the porous article is a silicon porous article. The fine pore particles of the silicon compound include, for example, a pulverized product of a gelated silica compound. As another form of the void layer, there is a void layer formed of a fibrous material such as nanofibers, and the fibrous material is entangled to form a layer including voids. The method for producing such a void layer is not particularly limited, but is, for example, the same as the void layer of a porous article in which the fine pore particles are chemically bonded to each other. In addition, as described above, it also includes void layers formed by using hollow nanoparticles or nano-clays, and void layers formed by using hollow nano-balloons or magnesium fluoride. The void layer may be a void layer made of a single constituent material or a void layer made of a plurality of constituent materials. The shape of the void layer may be a single shape or a plurality of voids of the above-described shape.

The void layer of the present invention is, for example, a layer formed by a porous article containing fine pore particles. The fine pore particles include, for example, a pulverized product of a gel compound. The porous article is, for example, chemically bonded to the pulverized products. In the void layer of the present invention, the form of the chemical bond (chemical bond) between the pulverized products is not particularly limited, and specific examples of the chemical bond include, for example, crosslinking. The method of chemically bonding the pulverized products together will be described in detail in the production method of the present invention.

The gel form of the gel compound is not particularly limited. The term " gel " generally refers to a state in which the solute has aggregated structures that lose their motility due to mutual interaction and solidify. Among the gels, in general, the wet gel includes a dispersion medium and has a structure in which the solute is uniform in the dispersion medium, and the xerogel removes the solvent to take a network structure in which the solute has a void It says. In the present invention, the gel compound may be, for example, a wet gel or a xerogel.

The gel-like compound may be, for example, a gelled product obtained by gelation of a monomer compound. The gel-like compound may be, for example, a gelated silicon compound. Specifically, the gel-like silicon compound may be, for example, a gelled substance in which the silicon compound of the monomer is bonded to each other, specifically, a gelled substance in which the silicon compound of the monomer is hydrogen-bonded or intermolecularly bonded to each other. The bonding may be, for example, bonding by dehydration condensation. The gelling method will be described later in the production method of the present invention.

In the void layer of the present invention, the volume average particle diameter indicating the particle size deviation of the fine pore particle is not particularly limited and may be, for example, 0.1 mu m or more, 0.2 mu m or more and 0.4 mu m or more, For example, not more than 2 탆, not more than 1.5 탆, and not more than 1 탆, and the range is, for example, 0.1 탆 to 2 탆, 0.2 탆 to 1.5 탆, and 0.4 탆 to 1 탆. The volume average particle diameter can be measured by, for example, a particle size distribution evaluation device such as a dynamic light scattering method or a laser diffraction method, and an electron microscope such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM) .

The particle size distribution of the fine pore particles is not particularly limited and may be, for example, from 50 to 99.9% by weight, from 80 to 99.8% by weight, from 90 to 99.7% by weight % Or 0.1 to 50% by weight, 0.2 to 20% by weight and 0.3 to 10% by weight of particles having a particle diameter of 1 to 2 占 퐉. The particle size distribution can be measured by, for example, a particle size distribution evaluation apparatus or an electron microscope.

In the void layer of the present invention, the kind of the gel-like compound is not particularly limited. As the gel-like compound, for example, a gel-like silicon compound can be exemplified. Hereinafter, the case where the gel-like compound is a gel-like silicon compound is described as an example, but the present invention is not limited thereto.

The crosslinking is, for example, a siloxane bond. The siloxane bond can be exemplified by a bond of T2, a bond of T3, and a bond of T4 shown below, for example. In the case where the void layer of the present invention has a siloxane bond, for example, any one kind of bonds may be used, any two kinds of bonds may be used, or all three kinds of bonds may be used. The more the ratio of T2 and T3 in the siloxane bond is, the greater the flexibility and the property inherent to the gel can be expected, but the film strength becomes weak. On the other hand, if the ratio of T4 in the siloxane bonds is large, the membrane strength tends to be manifested, but the pore size is reduced and the flexibility is discarded. Therefore, for example, it is preferable to change the ratio of T2, T3, and T4 depending on the application.

[Chemical Formula 1]

When the void layer of the present invention has the siloxane bond, the ratio of T2, T3 and T4 is, for example, T2: T3: T4 = 1: [1 to 100 ]: [0 to 50], 1: [1 to 80]: [1 to 40], and 1: [5 to 60]: [1 to 30].

The void layer of the present invention is preferably, for example, a siloxane-bonded silicon atom. As a specific example, the ratio of the unconjugated silicon atoms (that is, residual silanol) among the total silicon atoms contained in the void layer is, for example, less than 50%, 30% or less, and 15% or less.

When the gel-like compound is the gel-like silicon compound, the silicon compound of the monomer is not particularly limited. The silicon compound of the monomer may be, for example, a compound represented by the following formula (1). When the above-mentioned gelled silicon compound is a gelled product in which the silicon compound of the monomer is bonded to each other by hydrogen bonding or intermolecular force bonding, the monomers of formula (1) are bonded to each other through, for example, .

(2)

In the formula (1), for example, X is 2, 3 or 4, and R ¹ is a linear or branched alkyl group. The number of carbon atoms of R ¹ is, for example, 1 to 6, 1 to 4, and 1 to 2. Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group. The branched alkyl group includes, for example, an isopropyl group, . X is, for example, 3 or 4.

Specific examples of the silicon compound represented by the formula (1) include, for example, a compound represented by the formula (1 ') in which X is 3. In the following formula (1 '), R ¹ is the same as in the formula (1) and is, for example, a methyl group. When R ¹ is a methyl group, the silicon compound is tris (hydroxy) methylsilane. When X is 3, the silicon compound is, for example, a trifunctional silane having three functional groups.

(3)

Specific examples of the silicon compound represented by the above formula (1) include, for example, a compound wherein X is 4. In this case, the silicon compound is, for example, a tetrafunctional silane having four functional groups.

The silicon compound of the monomer may be, for example, a hydrolyzate of a silicon compound precursor. The silicon compound precursor may be any one capable of producing the silicon compound by, for example, hydrolysis, and specific examples include a compound represented by the following formula (2).

[Chemical Formula 4]

In the formula (2), for example, X is 2, 3 or 4,

R ¹ and R ² are each a linear or branched alkyl group,

R ¹ and R ² may be the same or different,

R ¹ may be the same or different when X is 2,

R ² may be the same or different.

Wherein X and R ¹ are, for example, it is the same as X and R ¹ in the formula (1). The above-mentioned R ² can be exemplified by, for example, R ^{1 in} the formula (1).

Specific examples of the silicon compound precursor represented by the formula (2) include a compound represented by the formula (2 ') in which X is 3, for example. In the following formula (2 '), R ¹ and R ² are the same as those in the formula (2), respectively. When R ¹ and R ² are methyl groups, the silicon compound precursor is trimethoxy (methyl) silane (hereinafter also referred to as "MTMS").

[Chemical Formula 5]

The silicon compound of the monomer is preferably the bifunctional silane in that it is excellent in low refractive index, for example. In addition, the silicon compound of the monomer is preferably the above tetrafunctional silane in that it has excellent strength (for example, scratch resistance). The silicon compound of the monomer as the raw material of the gel-like silicon compound may be used singly, or two or more kinds may be used in combination. As a specific example, the silicon compound of the monomer may include, for example, only the trifunctional silane, only the tetrafunctional silane, both the trifunctional silane and the tetrafunctional silane, Other silicon compounds may be included. When two or more kinds of silicon compounds are used as the silicon compound of the monomer, the ratio is not particularly limited and can be appropriately set.

The void layer may contain, for example, a catalyst for chemically bonding one kind or plural kinds of constituent units forming the fine void structure. The content of the catalyst is not particularly limited, but is, for example, 0.01 to 20% by weight, 0.05 to 10% by weight, or 0.1 to 5% by weight based on the weight of the constituent unit.

Further, the void layer may further include a crosslinking aid for indirectly bonding one kind or a plurality of kinds of constituent units forming the fine void structure, for example. The content of the crosslinking aid is not particularly limited and is, for example, 0.01 to 20% by weight, 0.05 to 15% by weight, or 0.1 to 10% by weight based on the weight of the constituent unit.

[Cover Layer]

In the present invention, the cover layer is not particularly limited. In the present invention, the " cover layer " is, for example, a layer (coating layer) for covering the gap layer and is, for example, a layer having an antiscratching property (overcoat layer).

In the present invention, the cover layer is formed directly on the void layer. As used herein, the term " directly formed " as used herein may be formed by coating the cover layer on the void layer, for example, as described later. However, the void layer and the cover layer may be separately prepared , And transferring the cover layer onto the gap layer.

The cover layer is, for example, a hydrocarbon-based solvent such as hexane or a cover layer-forming liquid comprising water as a solvent, from the viewpoint of suppressing the influence on the solvent resistance, because the void layer has low solvent resistance . The void layer is, for example, a cover layer composition liquid comprising water as a solvent. The composition in the above-mentioned composition liquid may be, for example, those exemplified in the composition (forming material) of the above-mentioned void layer.

The cover layer is, for example, a layer formed by coating a water-based paint. Thereby, since the cover layer is water-soluble, the material for forming the cover layer can further suppress the embedding of the structure of the void layer due to the high water repellency of the void layer. The aqueous paint is, for example, a coating liquid for a water solvent, and the coating liquid for the water solvent may be in the form of a solution or a dispersion. The concrete material for forming the water-base paint is not particularly limited and may be exemplified as the material for forming the void layer.

The cover layer is preferably in the form of containing at least one of a water-soluble crosslinking agent and a water-soluble polymer. If the water-repellent paint as a raw material of the cover layer is composed only of monomer or oligomer and has a low viscosity due to high water repellency of the void layer, cratering occurs during coating, and there is a possibility that a cover layer can not be formed on the void layer. On the other hand, by including a water-soluble crosslinking agent or a water-soluble polymer, the viscosity of the water-based paint becomes high, and cratering can be prevented. The water-soluble crosslinking agent and the water-soluble polymer are not particularly limited and, for example, water-soluble crosslinking agents and water-soluble polymers exemplified as the material for forming the void layer may be used. Examples of the water-soluble crosslinking agent include crosslinked products formed from at least one of monomers and oligomers of water-soluble alkoxysilane which is an inorganic organic hybrid (hereinafter sometimes referred to as "water-soluble silane crosslinked product"). The water-soluble silane crosslinking agent is not particularly limited and includes, for example, a silica compound crosslinked by the siloxane bond. For example, the bonding of T2, the bonding of T3, And the like.

[Chemical Formula 6]

Examples of the water-soluble polymer include acrylic, vinyl alcohol-based, silicone-based, polyester-based, polyurethane-based, and polyether-based polymers. Examples of such water-soluble polymers include silicon- And polymers of alkoxysilanes represented by the above formula (2). Particularly, a polyvinyl alcohol-based, polyurethane-based, self-crosslinking acrylic emulsion and the like are preferable in view of stability and high viscosity of the aqueous polymer solution.

(7)

It is preferable that at least one of the water soluble crosslinking agent and the water soluble polymer is contained in the cover layer so as to form a hydrogen bond with the constituent material of the air gap layer and improve the adhesion between the air gap layer and the cover layer . Furthermore, by including the silane monomer and / or the silane oligomer in the cover layer, it is possible to improve the adhesion by using the cover layer and the gap layer together.

At least one of the water-soluble crosslinking agent and the water-soluble polymer may be used alone, or a plurality of kinds may be used in combination (for example, mixing, lamination, etc.).

The cover layer is, for example, a layer formed by applying a cover layer raw material liquid containing the raw material of the cover layer on the void layer, drying the layer, and then performing at least one of heating and light irradiation. The cover layer raw material liquid may be, for example, a liquid containing a compound capable of decomposing by heating or light irradiation to generate a base (hereinafter simply referred to as a " base generating compound "), A liquid containing at least one of a monomer and an oligomer of silane, and a liquid containing at least one of the monomer and the oligomer of the water-soluble alkoxysilane and the base generating compound.

The base generating compound is not particularly limited and may be exemplified as a material for forming the void layer. Specifically, for example, a material capable of generating a basic catalyst by heat (a heat base generator) (Photo-base generator) that generates a basic catalyst by the action of a photoacid generator and the like, and is, for example, a photo-base generator. Examples of the thermal base generator include urea and the like. Examples of the photobase generators include 9-anthrylmethyl N, N-diethylcarbamate (trade name WPBG-018), (E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine (trade name WPBG-027), 1- 2-yl) ethyl imidazole carboxylate (trade name: WPBG-140), 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate (Trade name WPBG-165), 1,2-diisopropyl-3- [bis (dimethylamino) methylene] guanidinium 2- (3-benzoylphenyl) propionate (Trade name: WPBG-300), and 2- (9-oxo xanthene-2-yl) propionic acid 1,5,7-dicyclohexyl-4,4,5,5-tetramethylbiguanide (Trade name: HDPD-PB100: manufactured by Tokyo Chemical Industry Co., Ltd.) and 4-piperidinemethanol, Manufactured by Heraeus Co., Ltd.). The trade names including the above " WPBG " are all trade names of Wako Pure Chemical Industries, Ltd.

The monomer of the water-soluble alkoxysilane is not particularly limited and may be exemplified as the material for forming the void layer. Specifically, for example, the silicon compound represented by the formula (2) Examples of the oligomer of the water-soluble alkoxysilane include oligomers of the silicon compound represented by the formula (2).

[Chemical Formula 8]

By including, for example, the above-mentioned nucleating compound in the cover layer, for example, by a catalytic reaction using the photo-nucleating agent, a compound (for example, a monomer of the water-soluble alkoxysilane and / Oligomer, etc.) and the microporous particles of the void layer are chemically bonded (for example, crosslinking reaction), so that the adhesion between the cover layer and the void layer is further improved.

In the formation of the void layer and the cover layer, for example, after forming the cover layer after performing the strength improving step (void layer strength improving step) on the formed void layer as described later, The formed cover layer may be subjected to a strength improving step (a cover layer strength improving step). As described above, the gap layer strength improving step and the cover layer strength improving step may be separately performed. For example, before the gap layer strength improving step, the cover layer is formed and the cover layer strength improving step is performed The above-described void layer strength improving step may be carried out. That is, both of the above steps may be performed separately, or both steps may be performed at the same time. As a result, the microporous particles of the compound in the cover layer and the microporous particles of the gap layer can be simultaneously gelled, because the step of increasing the strength of the gap layer and the cover layer (aging step) are performed at the same time, The adhesion between the cover layer and the void layer is improved, and the scratch resistance of the cover layer is also improved.

The thickness of the cover layer is not particularly limited, but is, for example, 50 nm to 10000 nm, 100 nm to 5000 nm, 150 nm to 4000 nm, or 200 nm to 3000 nm.

The porosity of the cover layer is not particularly limited and is 10% by volume or less, preferably 9% by volume or less and 8% by volume or less, for example, from the viewpoint of improving scratch resistance. The porosity can be measured by a method based on the above-mentioned film density of the void layer.

The laminated optical film of the present invention is, for example, a roll. Further, the laminated optical film of the present invention may further include a resin film, for example, as described above, and the void layer may be formed on the elongated resin film. In this case, another long film may be laminated on the laminated optical film of the present invention, and another laminated optical film (for example, a laminate, a release film , A surface protective film, or the like) and then wound on a roll.

The method for producing the laminated optical film of the present invention is not particularly limited, and for example, it can be produced by the production method of the present invention shown below.

[2. Outline and Details of Manufacturing Method of Laminated Optical Film]

The method for producing a laminated optical film of the present invention is a method for producing a laminated optical film, which comprises the steps of: forming an air gap layer on the resin film; and forming the cover layer on the air gap layer And a control unit. Further, unless otherwise stated, the description of the laminated optical film of the present invention can be used for the manufacturing method of the present invention.

[2.1 Outline of Blank Layer Formation Process]

In the method for producing a laminated optical film of the present invention, the void layer is, for example, a porous article in which the fine pore particles are chemically bonded to each other. In the void layer forming step, for example, Are chemically bonded. The method for producing a laminated optical film of the present invention is a method for producing a laminated optical film, for example, as described above, which comprises a step of preparing a containing liquid for producing a containing liquid containing the fine pore particles, And a drying step of drying the coated liquid. In the void layer forming step, for example, the porous particles may be formed by chemically bonding the fine pore particles to one another. In the void layer forming step, the voids may be formed by chemically bonding the fine pores with each other by the action of a catalyst. In this case, the catalyst is, for example, a basic catalyst, and the containing liquid includes a base generator that generates the basic catalyst by light or heat. The method may further include a chemical treatment step of chemically bonding the fine pore particles by light irradiation or heating in the pore layer forming step to form the pore layer, (Aging step) may be carried out. As another form of the void layer, there is a void layer formed of a fibrous material such as nanofibers, and the fibrous material is entangled to form a layer including voids. In the production method, it is the same as the fine pore particle. Also included are void layers formed using hollow nanoparticles or nano-clays, and void layers formed using hollow nano-balloons or magnesium fluoride.

The liquid containing the fine pore particles (hereinafter sometimes referred to as the " fine pore particle containing liquid " or simply " containing liquid ") is not particularly limited. For example, a suspension containing the fine pore particles to be. In the following description, mainly, the case where the microporous particle is a pulverized product of a gelated compound and the void layer is a porous article (preferably, a porous silicon body) containing a pulverized product of the gelated compound. However, the present invention can be carried out in the same manner even when the fine pore particles are other than the pulverized product of the gel compound.

According to the production method of the present invention, for example, a void layer exhibiting excellent low refractive index is formed. The reason for this is presumed as follows, for example, but the present invention is not limited to this conjecture.

Since the fine pore particles used in the production method of the present invention are obtained by, for example, pulverizing the gel-like silicon compound, the three-dimensional structure of the gel-like silicon compound before pulverization is dispersed in a three-dimensional basic structure. Further, in the production method of the present invention, a precursor of a porous structure based on the three-dimensional basic structure is formed by coating a pulverized product of the gel-like silicon compound on the substrate. In short, according to the production method of the present invention, a new porous structure formed from the above-mentioned pulverized product of the three-dimensional basic structure, which is different from the three-dimensional structure of the gelated silicon compound, is formed. For this reason, the finally obtained void layer can exhibit a low refractive index which functions, for example, to the same extent as the air layer. Further, in the production method of the present invention, for example, since the microporous particles are chemically bonded to each other, the new three-dimensional structure is immobilized. Therefore, the finally obtained void layer has a structure having voids, but sufficient strength and flexibility can be maintained. As described above, the void layer obtained by the production method of the present invention is useful, for example, in terms of the function of low refractive index as a substitute for the air layer and also in strength and flexibility. Further, in the case of the above-described air layer, it is necessary to form an air layer between the members by, for example, forming a gap between the member and the member by interposing a spacer or the like therebetween. However, the void layer obtained by the production method of the present invention can exhibit low refractive index, which functions to the same extent as that of the air layer, by, for example, disposing the void layer at a desired site. Therefore, as described above, it is possible to easily and easily provide the optical member with a low refractive index that functions to the same degree as that of the air layer, as compared with the case where the air layer is formed.

The void layer formed by the production method of the present invention may have a hole structure (porous structure) as described above, for example, and the hole structure may be continuous. The fogged structure means, for example, that the hole structure is arranged three-dimensionally in the above-mentioned silicon porous body, and it may be said that the internal voids of the hole structure are continuous. When the porous material has a softening structure, it is possible to increase the porosity occupied in the bulk material, but when the dusting particle such as hollow silica is used, a softening structure can not be formed. On the other hand, in the case where the void layer of the present invention has, for example, silica sol particles (pulverized product of a gel-like silicon compound forming a sol), the particles have a three-dimensional water- It is possible to easily form a softened structure by depositing or depositing the above-mentioned water-absorbing particles in a film (a coating film of a sol containing a pulverized product of the gel-like silicon compound). Further, it is preferable that the void layer of the present invention more preferably forms a monolith structure in which the soft structure has a plurality of pore distributions. The monolith structure refers to, for example, a hierarchical structure existing as a structure in which fine nano-sized voids exist, and a soft-nano structure in which copper nano voids are aggregated. In the case of forming the monolith structure, for example, a high porosity can be imparted to the coarse fume gap while the film strength is imparted to the fine gap, so that the film strength and the high porosity can be both satisfied. To form these monolith structures, it is preferable to first control the pore distribution of the generated pore structure in the gel (gel-like silicon compound) before the pulverization with the silica sol particles. Further, for example, when the gel-like silicon compound is pulverized, the monolith structure can be formed by controlling the particle size distribution of the silica sol particles after the pulverization to a desired size.

In the void layer forming step, for example, the microporous particles are chemically bonded to each other by a catalytic reaction using a photo base generating agent to form the void layer. Further, for example, since the base catalyst generated from the photo-base generator remains in the precursor, the chemical bonds between the fine pore particles (for example, crosslinking Reaction) proceeds further. Thus, it is considered that the strength of the void layer is improved. As a specific example, when the fine pore particle is a fine pore particle of a silicon compound (for example, a pulverized product of a gelated silica compound) and a residual silanol group (OH group) is present in the pore layer, It is considered that they are chemically bonded by a crosslinking reaction. However, this description is also an example, and the present invention is not limited thereto.

[2.2 Outline of the process of forming the cover layer]

Further, in the manufacturing method of the present invention, the cover layer forming step may be, for example, a cover layer raw material solution coating step of directly coating the cover layer raw material liquid containing the raw material of the cover layer on the gap layer, And a cover layer raw material liquid drying step of drying the cover layer raw material liquid containing the raw material of the coated cover layer, wherein after the covering layer raw material liquid drying step, the chemical forming the cover layer by at least one of heating and light irradiation And a strength improving step of forming the cover layer by heating at 80 DEG C or lower for 1 hour after the cover layer raw material liquid drying step.

The cover layer raw material liquid (hereinafter sometimes simply referred to as " raw material liquid ") is not particularly limited and may be, for example, a compound capable of decomposing by heating or light irradiation to generate a base A liquid containing at least one of a monomer and an oligomer of a water-soluble alkoxysilane, and the cover layer raw material liquid is a liquid containing at least one of the monomer and the oligomer of the water-soluble alkoxysilane At least one of them may be included. Examples of the base generating compound include the base generating compounds exemplified in the cover layer of the laminated optical film of the present invention. Examples of the monomer and oligomer of the water-soluble alkoxysilane include the above- In the layer, examples of the above-mentioned water-soluble alkoxysilane monomers and oligomers are mentioned.

The manufacturing method of the present invention can be arbitrarily explained without any description of the laminated optical film of the present invention.

In the production method of the present invention, the precursor of the fine pore particle, the monomer compound and the monomer compound can be used in the description of the pore layer of the present invention.

[2.3 Details of Manufacturing Method of Laminated Optical Film]

The method for producing the laminated optical film of the present invention can be carried out, for example, as follows, but is not limited thereto.

[2.3.1 Details of Bubble Layer Formation Process]

Hereinafter, the void layer forming step of the present invention will be described first. For example, the void layer formed of the porous material of silica particles will be described, but the method of forming the void layer is not limited thereto.

[2.3.1.1 Production process of a containing liquid]

The method for producing a laminated optical film of the present invention has, for example, a process for producing a containing liquid for producing a containing liquid containing the above-described fine pore particles as described above. When the fine pore particle is a fine pore particle of a silicon compound, it includes a ground product of a gelated silica compound. The pulverized product is obtained, for example, by pulverizing a gel-like silicon compound (gel-like silicon compound). By the grinding of the gel-like silica compound, the three-dimensional structure of the gel-like compound is broken as described above and dispersed into the three-dimensional basic structure.

Hereinafter, the production of the gel-like silica compound by gelation of the silicon compound and the preparation of the ground product by the grinding of the gel-like silica compound will be described by way of example, but the present invention is not limited to the following examples.

The gelation of the silicon compound can be carried out, for example, by hydrogen bonding or intermolecular force bonding of the silicon compound.

The silicon compound includes, for example, the silicon compound represented by the formula (1) described in the void layer of the present invention.

[Chemical Formula 9]

Since the silicon compound of the formula (1) has a hydroxyl group, hydrogen bonding or intermolecular force bonding between the monomers of the formula (1) can be carried out through, for example, respective hydroxyl groups.

The silicon compound may be a hydrolyzate of the silicon compound precursor as described above. For example, the silicon compound precursor represented by the formula (2) described in the void layer of the present invention may be hydrolyzed .

[Chemical formula 10]

The method of hydrolyzing the silicon compound precursor is not particularly limited and can be carried out, for example, by a chemical reaction in the presence of a catalyst. Examples of the catalyst include acids such as oxalic acid and acetic acid. The hydrolysis reaction can be carried out, for example, by slowly dropwise adding an aqueous solution of oxalic acid to a mixture of the silicon compound and dimethylsulfoxide (for example, a suspension) under a room temperature environment, followed by stirring for about 30 minutes have. When the silicon compound precursor is hydrolyzed, for example, the alkoxyl group of the silicon compound precursor is completely hydrolyzed, whereby subsequent gelation, aging, heating and immobilization after formation of the pore structure can be more efficiently expressed.

The gelation of the silicon compound can be carried out, for example, by a dehydration condensation reaction between the monomers. The dehydration condensation reaction is preferably carried out in the presence of a catalyst, and examples of the catalyst include an acid catalyst such as hydrochloric acid, oxalic acid and sulfuric acid, and ammonia, potassium hydroxide, sodium hydroxide, ammonium hydroxide , And dehydration condensation catalysts such as a base catalyst of a dehydration condensation catalyst. The dehydration condensation catalyst is particularly preferably a base catalyst. In the dehydration condensation reaction, the amount of the catalyst to be added to the silicon compound is not particularly limited, and the catalyst may be used in an amount of, for example, 0.1 to 10 mol, 0.05 to 7 mol, 5 moles.

The gelation of the silicon compound is preferably carried out, for example, in a solvent. The ratio of the monomer compound in the solvent is not particularly limited. The solvent may be, for example, dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP), N, N-dimethylacetamide (DMAc), dimethylformamide (DMF) , Acetonitrile (MeCN), ethylene glycol ethyl ether (EGEE), and the like. The solvent may be, for example, one kind, or two or more kinds of solvents may be used in combination. The solvent used for the gelation is hereinafter also referred to as " gelling solvent ".

The conditions for the gelation are not particularly limited. The treatment temperature for the solvent containing the monomer compound is, for example, 20 to 30 ° C, 22 to 28 ° C and 24 to 26 ° C, and the treatment time is, for example, 1 to 60 minutes, Min, 10 to 30 minutes. When the dehydration condensation reaction is carried out, the treatment conditions are not particularly limited, and examples thereof may be used. By performing the gelation, for example, siloxane bonds are grown to form silica primary particles, and the reaction proceeds further, whereby the primary particles are arranged in a columnar phase to form a gel having a three-dimensional structure.

The gelled silica compound obtained by the gelation is preferably subjected to an aging treatment after the gelation reaction. By the above aging treatment, for example, primary particles of a gel having a three-dimensional structure obtained by gelation can be further grown, whereby the size of the particles themselves can be increased. As a result, the size of the neck portion The contact state can be increased from point contact to surface contact. The gel subjected to the aging treatment as described above can increase the strength of the gel itself, for example, and consequently improve the strength of the three-dimensional basic structure after the grinding. Thus, for example, in the drying step after coating the pulverized product, the pore size of the pore structure in which the three-dimensional basic structure is deposited can be inhibited from shrinking with evaporation of the solvent in the drying process.

The aging treatment can be carried out, for example, by incubating the gelated silica compound at a predetermined temperature for a predetermined time. The predetermined temperature is not particularly limited and the upper limit may be 80 占 폚 or lower, 75 占 폚 or lower, 70 占 폚 or lower, for example, 30 占 폚 or higher, 35 占 폚 or higher, For example, 30 to 80 캜, 35 to 75 캜, and 40 to 70 캜. The predetermined time is not particularly limited and the lower limit may be, for example, 5 hours or more, 10 hours or more, 15 hours or longer, and the upper limit may be, for example, 50 hours or shorter, 40 hours or shorter, 30 hours or shorter And the range is, for example, 5 to 50 hours, 10 to 40 hours, and 15 to 30 hours. For the optimum conditions of aging, for example, the main purpose is to increase the size of the primary silica particles and to increase the contact area of the neck portion. Furthermore, if the aging temperature is too high, for example, the solvent will volatilize excessively and the pores having a three-dimensional pore structure may be decomposed by the concentration of the coating solution (gel solution) There is a possibility that problems such as the problem of finding On the other hand, for example, when the aging temperature is too low, not only the above-described effect due to aging can not be sufficiently obtained but also the temperature deviation over time of the mass production process increases, .

The above-mentioned aging treatment may be carried out, for example, by using the same solvent as the gelling treatment, and specifically, it is preferable that the aging treatment is carried out directly on the reactant after the gelation treatment (that is, the solvent containing the gelated silica compound) Do. The number of moles of the residual silanol group contained in the gel (the gelated silica compound, for example, the gelated silicon compound) having undergone the aging treatment after the gelation is, for example, , The upper limit is, for example, 1% or less, and the lower limit is, for example, 50% or more, 40% or more, 30% or more, Or less and 3% or less and 5% or less, and the range is, for example, 1 to 50%, 3 to 40%, and 5 to 30%. For the purpose of increasing the hardness of the gel, for example, the lower the number of moles of the residual silanol group is, the more preferable. If the number of moles of the silanol group is too high, there is a possibility that the void structure can not be maintained until, for example, the precursor of the porous silicon body is crosslinked. On the other hand, when the number of moles of the silanol group is too low, for example, in the step of producing the microporous particle-containing liquid (for example, a suspension) and / or the subsequent step, There is a possibility that sufficient film strength can not be given. The above is an example of a silanol group, but when the silicon compound of the monomer is modified with various reactive functional groups, the same phenomenon can be applied to each functional group.

After the silicon compound is gelated in the gelation solvent, the obtained gelated silica compound is pulverized. The pulverization may be carried out, for example, by grinding the gel-like silica compound in the gelling solvent as it is, or after the gelling solvent is replaced with another solvent, the gel-like silica compound in the other solvent is pulverized Processing may be performed. Further, for example, when the catalyst used in the gelation reaction and the solvent used are still present after the aging step, when the gelation (pot life) of the solution with time passes and the drying efficiency is lowered during the drying step, . The other solvent is hereinafter also referred to as " solvent for grinding ".

The pulverizing solvent is not particularly limited, and for example, an organic solvent may be used. The organic solvent includes, for example, a solvent having a boiling point of 130 占 폚 or less, a boiling point of 100 占 폚 or less, and a boiling point of 85 占 폚 or less. Specific examples include isopropyl alcohol (IPA), ethanol, methanol, butanol, propylene glycol monomethyl ether (PGME), methylcellosolve, acetone, dimethylformamide (DMF) and the like. The pulverizing solvent may be, for example, one kind or two or more types of pulverizing solvents.

The combination of the gelling solvent and the pulverizing solvent is not particularly limited and includes, for example, a combination of DMSO and IPA, a combination of DMSO and ethanol, DMSO and methanol, DMSO and butanol. By replacing the gelling solvent with the grinding solvent in this manner, a more uniform coating film can be formed, for example, in the formation of a coating film described later.

The grinding method of the gelated silica compound is not particularly limited and may be, for example, an ultrasonic homogenizer, a high-speed homogenizer, a grinding apparatus using other cavitation phenomena, or a grinding apparatus . A device for performing media milling such as a ball mill physically destroys the pore structure of the gel at the time of milling, while the cavitation type milling device preferable for the present invention such as a homogenizer is, for example, , The silica particle bonding surface of the relatively weak bonding already contained in the gel three-dimensional structure is peeled by a high shear force because of the medialess method. Thus, the obtained sol-dimensional structure can maintain, for example, a void structure having a particle size distribution within a certain range, and can regenerate the void structure by deposition during coating and drying. The conditions for the pulverization are not particularly limited, and it is preferable that the gel can be pulverized without volatilizing the solvent, for example, by giving an instantaneous high-speed flow. For example, it is preferable to pulverize to obtain a pulverized product of the particle size deviation (for example, volume average particle size or particle size distribution) as described above. If the working amount such as the grinding time and the strength is insufficient, for example, there is a possibility that the fine particles remain and the dense pores can not be formed, and the appearance defects also increase, so that high quality can not be obtained. On the other hand, when the working amount is excessive, for example, fine sol particles become smaller than the desired particle size distribution, and the size of the pores deposited after coating and drying becomes finer, which may be lower than the desired porosity.

As described above, a liquid (for example, a suspension) containing the fine pore particles (for example, pulverized product of the gelated silica compound) can be prepared. Further, a liquid containing the fine pore particles and the catalyst can be prepared by adding a catalyst that chemically bonds the fine pore particles after the liquid containing the fine pore particles is produced or during the manufacturing process . The addition amount of the catalyst is not particularly limited, but is, for example, 0.01 to 20% by weight, 0.05 to 10% by weight, or 0.1 to 5% by weight based on the weight of the fine pore particles. The catalyst may be, for example, a catalyst promoting cross-linking between the fine pore particles. As the chemical reaction for chemically bonding the fine pore particles, it is preferable to use a dehydration condensation reaction of the residual silanol group contained in the silica sol molecule. By accelerating the reaction of the hydroxyl groups of the silanol group with the catalyst, it is possible to form a continuous film which cures the void structure in a short time. Examples of the catalyst include a photoactive catalyst and a thermally active catalyst. According to the above-described photoactive catalyst, for example, the fine pore particles can be chemically bonded (for example, crosslinked) in the void layer forming step without heating. According to this, for example, in the void layer forming step, since the contraction of the entire void layer does not occur well, a higher porosity can be maintained. Further, in addition to or instead of the catalyst, a substance (catalyst-generating agent) that generates a catalyst may be used. For example, a substance (a photocatalyst generating agent) that generates a catalyst by light may be used in addition to or instead of the photoactive catalyst. In place of or in place of the thermally active catalyst, (Thermal catalyst generating agent) may be used. Examples of the photocatalyst generating agent include, but are not particularly limited to, a photoacid generator (a substance that generates a basic catalyst by light irradiation), a photoacid generator (a substance that generates an acidic catalyst by light irradiation) , And a photobase generator is preferable. Examples of the photobase generators include 9-anthrylmethyl N, N-diethylcarbamate (trade name WPBG-018), (E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine (trade name WPBG-027), 1- 2-yl) ethyl imidazole carboxylate (trade name: WPBG-140), 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate (Trade name WPBG-165), 1,2-diisopropyl-3- [bis (dimethylamino) methylene] guanidinium 2- (3-benzoylphenyl) propionate (Trade name: WPBG-300), and 2- (9-oxo xanthene-2-yl) propionic acid 1,5,7-dicyclohexyl-4,4,5,5-tetramethylbiguanide (Trade name: HDPD-PB100: manufactured by Tokyo Chemical Industry Co., Ltd.) and 4-piperidinemethanol, Manufactured by Heraeus Co., Ltd.). The trade names including the above " WPBG " are all trade names of Wako Pure Chemical Industries, Ltd. Examples of the photo acid generator include triallylsulfonyl compounds and the like. The catalyst for chemically bonding the fine pore particles to each other is not limited to the photoactive catalyst and the photocatalyst generating agent but may be, for example, a thermal catalyst or a thermal catalyst generating agent such as urea. Examples of the catalyst for chemically bonding the fine pore particles include base catalysts such as potassium hydroxide, sodium hydroxide and ammonium hydroxide, and acid catalysts such as hydrochloric acid, acetic acid and oxalic acid. Among these, a base catalyst is preferred. The catalyst or the catalyst generating agent for chemically bonding the fine pore particles to each other may be added to a solution of sol particles (for example, a suspension) containing the pulverized product (fine pore particles) immediately before coating , Or a mixed solution obtained by mixing the catalyst or the catalyst generating agent in a solvent. The mixed solution may be, for example, a coating solution directly added to and dissolved in the sol solution, a solution in which the catalyst or the catalyst generating agent is dissolved in a solvent, or a dispersion in which the catalyst or the catalyst generating agent is dispersed in a solvent. The solvent is not particularly limited, and examples thereof include water, a buffer, various organic solvents, and the like.

Further, for example, when the fine pore particle is a pulverized product of a gel-like silicon compound obtained from a silicon compound containing at least trifunctional saturated bonding functional groups, a solution containing the fine pore particles is prepared, During the process, a crosslinking aid for indirectly bonding the fine pore particles may be further added. This crosslinking aid enters between the particles, and the particles and the crosslinking aid interact with each other or bond with each other, so that the particles slightly distant from each other can be bonded together, and the strength can be efficiently increased. The crosslinking aid is preferably a polyfunctional silane monomer. Concretely, the polyfunctional silane monomer has, for example, an alkoxysilyl group of 2 or more and 3 or less, a chain length between alkoxysilyl groups of 1 to 10 carbon atoms, or an element other than carbon. Examples of the crosslinking aid include bis (trimethoxysilyl) ethane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis Bis (trimethoxysilyl) propane, bis (trimethoxysilyl) propane, bis (triethoxysilyl) butane, bis (trimethoxysilyl) Bis (trimethoxysilyl) hexane, bis (trimethoxysilyl) hexane, bis (trimethoxysilyl) -N-butyl-N-propyl-ethane-1,2-diamine, tris- Silylpropyl) isocyanurate, and tris- (3-triethoxysilylpropyl) isocyanurate. The amount of the crosslinking aid to be added is not particularly limited and is, for example, 0.01 to 20% by weight, 0.05 to 15% by weight, or 0.1 to 10% by weight based on the weight of the fine pore particles of the silicon compound.

[2.3.1.2 Details of coating process]

Next, a liquid (for example, a suspension) containing the fine pore particles is coated on a resin film (hereinafter also referred to as " substrate ") (coating step). As the coating, for example, various coating methods described below may be used, and the present invention is not limited thereto. A coating liquid containing the fine pore particles and the catalyst can be formed by directly coating a liquid containing the fine pore particles (for example, a pulverized product of a gelated silica compound) on the resin film. The coating film may be, for example, a coating layer. Hereinafter, the coating film (coating layer) may be referred to as an " uncured film ". By forming the coating film (uncrosslinked film), for example, the pulverized product in which the three-dimensional structure is destroyed is settled and deposited, whereby a new three-dimensional structure is constructed. In addition, for example, the containing liquid containing the fine pore particles may not include a catalyst for chemically bonding the fine pore particles. For example, as will be described later, the void layer forming step may be carried out while spraying or spraying a catalyst for chemically bonding the fine pore particles to the coating film (uncrosslinked film). However, it is preferable that the containing liquid containing the fine pore particles includes a catalyst for chemically bonding the pore particles, and by the action of the catalyst contained in the pore film (uncrosslinked film) May be chemically bonded to form the porous body (void layer).

The solvent (hereinafter, also referred to as " coating solvent ") is not particularly limited and, for example, an organic solvent may be used. The organic solvent includes, for example, a solvent having a boiling point of 130 캜 or less. As specific examples, for example, IPA, ethanol, methanol, butanol, and the like can be used, and the same solvent as the above-mentioned pulverizing solvent can be used. When the present invention includes a step of pulverizing the gel-like silica compound, in the step of forming the coating film (uncrosslinked film), for example, the pulverizing solvent containing the pulverized product of the gel- It may be used as it is.

In the coating step, it is preferable that the pulverized product (hereinafter also referred to as " sol particle liquid ") on a sol dispersed in the solvent is coated on the substrate. The sol liquid of the present invention can be continuously formed by, for example, coating and drying on a substrate, followed by chemical crosslinking to form a void layer having a film strength of a certain level or higher. The term " sol " in the present invention refers to a state in which silica sol particles having a nano three-dimensional structure retaining a part of the pore structure are dispersed in a solvent to show fluidity by pulverizing the three-dimensional structure of the gel.

The concentration of the pulverized product in the solvent is not particularly limited and is, for example, 0.3 to 50% (v / v), 0.5 to 30% (v / v), and 1.0 to 10% (v / v) . If the concentration of the pulverized product is excessively high, for example, the fluidity of the solution of the sol particles is remarkably lowered, and there is a possibility of generating aggregates and coating stripes at the time of coating. On the other hand, if the concentration of the pulverized product is too low, for example, not only a considerable time is taken to dry the solvent of the sol liquid, but also the residual solvent immediately after drying becomes high, and thus the porosity may be lowered .

The physical properties of the sol are not particularly limited. The shear viscosity of the sol is, for example, a viscosity of 100 cPa 占 퐏 or less, a viscosity of 10 cPa 占 퐏 or less, and a viscosity of 1 cPa 占 퐏 or less at a shear rate of 10001 / s. If the shear viscosity is excessively high, for example, there is a possibility that a problem such as a decrease in the transfer rate of the gravure coating occurs due to the occurrence of coating streaks. On the other hand, if the shear viscosity is too low, for example, the thickness of the wet coating (coating) at the time of coating can not be increased, and a desired thickness may not be obtained after drying.

The coating amount of the ground product with respect to the substrate is not particularly limited and may be suitably set, for example, according to the desired thickness of the silicon porous body. As a specific example, in the case of forming the above-mentioned silicon porous article having a thickness of 0.1 to 1000 占 퐉, the amount of the pulverized product coated on the substrate is 0.01 to 60000 占 퐂, 0.1 to 5000 占 퐂 , And 1 to 50 쨉 g. The preferable coating amount of the sol liquid is related to the concentration of the liquid, the coating method, and the like. Therefore, it is difficult to uniquely define it, but from the viewpoint of productivity, it is preferable to coat it with as thin layer as possible. If the coating amount (coating amount) is excessively large, for example, there is a high possibility that the solvent is dried in the drying furnace before volatilization. Thereby, the nanocrystal sol particles precipitate and deposit in the solvent, and the solvent is dried before forming the void structure, so that the formation of voids is inhibited and the porosity may be greatly lowered. On the other hand, if the coating amount is too small, there is a possibility that the risk that coating cratering will occur due to the unevenness of the substrate surface and the hydrophilic / hydrophilic property may be increased.

[2.3.1.3 Details of drying process]

Further, the production method of the present invention has, for example, a drying step of drying a coated film (uncrosslinked film) produced by coating a microporous particle-containing liquid, as described above. The drying treatment in the drying step not only removes the solvent (solvent contained in the sol particle liquid) in the coating film (uncrosslinked film), but also precipitates the sol particles during the drying treatment Thereby forming a void structure. The drying treatment may be carried out at a temperature of, for example, 0.1 to 30 minutes, 0.2 to 10 minutes, or 0.3 to 10 minutes, for example, 50 to 250 ° C, 60 to 150 ° C, Three minutes. With respect to the drying treatment temperature and time, for example, in terms of continuous productivity and the expression of a high porosity, it is preferable to be lower and shorter. If the conditions are too strict, for example, when the substrate is a resin film, the substrate is brought close to the glass transition temperature of the substrate, so that the substrate is stretched in the drying furnace, and defects such as cracks There is a possibility of occurrence. On the other hand, when the condition is excessively loose, for example, since the residual solvent is contained at the timing of leaving the drying furnace, there is a possibility that an apparent problem such as occurrence of a scratch flaw occurs in the next step when the roll is struck.

The drying treatment may be, for example, natural drying, heat drying, or vacuum drying. The drying method is not particularly limited, and general heating means can be used, for example. The heating means may be, for example, a hot air heater, a heating roll, or a far infrared heater. Among them, it is preferable to use heat drying when it is premised that the product is continuously produced industrially. With respect to the solvent to be used, a solvent having a low surface tension is preferable for the purpose of suppressing generation of shrinkage stress accompanying solvent volatilization at the time of drying and thus cracking of the void layer (the porous silicon porous body). Examples of the solvent include, but are not limited to, lower alcohols such as isopropyl alcohol (IPA), hexane, and perfluorohexane. In addition, a small amount of a perfluoro surfactant or a silicone surfactant may be added to the IPA to lower the surface tension.

Further, in the method for producing a laminated optical film of the present invention, for example, the fine pore particles are chemically bonded to each other by the action of the catalyst to form the porous article (void layer) (void layer forming step). Thus, for example, the three-dimensional structure of the pulverized product in the coating film (uncured film) is fixed. When the conventional sintering is carried out, for example, a high-temperature treatment at a temperature of 200 ° C or higher causes dehydration condensation of silanol groups and formation of siloxane bonds. In the present invention, by reacting various additives which catalyze the dehydration condensation reaction described above, for example, it is possible to obtain a film having a relatively low drying temperature of around 100 캜 and a short drying time of less than several minutes The void structure can be continuously formed and immobilized by the treatment time.

The method of chemically bonding is not particularly limited and may be appropriately determined depending on the kind of the gel-like silicon compound, for example. As a specific example, the chemical bonding can be carried out, for example, by chemical cross-linking among the pulverized products, and in addition, inorganic particles such as titanium oxide and the like can be added to the pulverized product When added, it is also conceivable to chemically crosslink the inorganic particles and the pulverized product. In some cases, a biocatalyst such as an enzyme is supported, and the crushed product is chemically crosslinked with a site other than the catalytic active site. Therefore, the present invention is not limited to these, for example, application development of an organic-inorganic hybrid cavity layer, a host guest cavity layer, etc., as well as a cavity layer (silicon porous article) forming the sol particles.

No particular limitation is imposed on the chemical reaction (void layer formation step) in the presence of the catalyst at which stage in the production method of the present invention. For example, in the method for producing a laminated optical film of the present invention, the drying step may also serve as the void layer forming step. Further, for example, after the drying step, the void layer forming step for chemically bonding the fine pore particles to each other by the action of the catalyst may be performed. For example, as described above, the catalyst may be a photoactive catalyst, and the porous material (void layer) may be formed by chemically bonding the fine pore particles by light irradiation in the void layer forming step . In addition, the catalyst may be a thermally active catalyst, and the porous material (void layer) may be formed by chemically bonding the fine pore particles by heating in the void layer forming step.

The chemical reaction may be carried out, for example, by irradiating or heating the coating film containing the catalyst or the catalyst generating agent previously added to the sol particle solution (for example, a suspension) Irradiating or heating the catalyst, or irradiating or heating the catalyst or the catalyst generating agent while spraying the catalyst. The amount of accumulated light in the light irradiation is not particularly limited, but is, for example, 200 to 800 mJ / cm 2, 250 to 600 mJ / cm 2, or 300 to 400 mJ / cm 2 in terms of @ 360 nm. The cumulative light quantity of not less than 200 mJ / cm 2 is preferable from the viewpoint of insufficient irradiation amount and preventing degradation due to light absorption of the catalyst generating agent from proceeding insufficiently. Further, from the viewpoint of preventing damage to the substrate under the gap layer to prevent heat wrinkling, an integrated amount of light of 800 mJ / cm 2 or less is preferable. The heating temperature is, for example, 50 to 250 DEG C, 60 to 150 DEG C, and 70 to 130 DEG C, and the heating time is, for example, 0.1 to 30 minutes , 0.2 to 10 minutes, and 0.3 to 3 minutes. Alternatively, the step of drying the sol liquid (for example, suspension) coated as described above may also serve as a step of carrying out a chemical reaction in the presence of the catalyst. That is, in the step of drying the coated sol particles (for example, suspension), the pulverized materials (fine pore particles) may be chemically bonded by a chemical reaction in the presence of the catalyst. In this case, the pulverized material (fine particle) may be more firmly bonded to each other by further heating the coating film after the drying step. The chemical reaction in the presence of the catalyst may also occur in the step of preparing the microporous particle-containing liquid (for example, a suspension) and the step of coating the microporous particle-containing liquid. However, this conjecture does not limit the present invention at all. With respect to the solvent to be used, for example, a solvent having a low surface tension is preferable for the purpose of suppressing generation of shrinkage stress accompanying solvent volatilization upon drying and accordingly cracking of the cavity layer. For example, lower alcohols such as isopropyl alcohol (IPA), hexane, perfluorohexane, and the like are exemplified, but are not limited thereto.

[2.3.1.4 Details of strength improvement process (aging process)]

Further, the void layer of the present invention may be subjected to a strength improving step (aging step) for improving strength by, for example, treatment such as heating aging. In the strength improving step (aging step), for example, the void layer of the present invention may be heated. The temperature in the strength improving step (aging step) is, for example, 30 to 80 ° C, 35 to 70 ° C, 40 to 60 ° C, or 50 to 60 ° C. The time for performing the aging step is, for example, 1 to 50 hr, 3 to 40 hr, 5 to 30 hr, or 7 to 25 hr. In the aging step, for example, by setting the heating temperature at a low temperature, it is possible to improve the adhesive peel strength while suppressing the shrinkage of the void layer, and to achieve both high porosity and high strength.

[2.3.2 Details of the cover layer forming process]

Next, the cover layer is directly formed on the gap layer (cover layer forming step). In the cover layer forming step, the cover layer may be formed on the cavity layer by bonding the cover layer onto the cavity layer. The cover layer forming step is not particularly limited and includes, for example, the cover layer raw material solution coating step, the cover layer raw material liquid drying step, and the cover layer strength improving step (aging step).

[2.3.2.1 Details of Coating Layer Raw Material Liquid Coating Process]

First, for example, the cover layer raw material liquid containing the raw material of the cover layer is directly coated on the gap layer (cover layer raw material liquid coating step). The cover layer raw material liquid coating process may use the same coating process as the coating process in the void layer forming process. In the cover layer raw material solution coating process, a solvent exemplified for the coating solvent in the void layer forming step may be used as the coating solvent.

[2.3.2.2 Details of drying process of raw material liquid for cover layer]

Next, for example, the liquid containing the material of the cover layer coated is dried (covering layer raw material liquid drying step). The temperature and time of the drying treatment may be the temperature and the time exemplified in the drying step in the void layer forming step.

In the cover layer forming step, after the cover layer raw material liquid drying step, the cover layer is formed by at least one of heating and light irradiation. In the cover layer forming step, for example, the compound in the cover layer and the micropores in the gap layer may be chemically bonded to each other by light irradiation, and the catalyst is a thermally active catalyst, In the layer forming step, the compound in the cover layer and the fine pore particle may be chemically bonded by heating. The light irradiation amount in the light irradiation, the temperature of the heat treatment, and the heating time are not particularly limited and may be the same as those exemplified in the void layer forming step.

[2.3.2.3 Details of strength improvement process]

In the cover layer forming step, the strength of the formed cover layer may be further improved by heating at 80 DEG C or lower for 1 hour or more (strength increasing step (aging step)). The upper limit of the heating temperature is, for example, 80 DEG C or lower, for example, 70 DEG C or lower, for example, 60 DEG C or lower, the lower limit of the heating temperature is 30 DEG C or higher, For example, it is 35 ° C or more, for example, 40 ° C or more, and the range is 30 ° C to 80 ° C, for example, 35 ° C to 70 ° C, Or more and 60 占 폚 or less. The lower limit of the heating time is 1 hr (hour) or more, for example, 3 hr (hour) or longer, for example, 4 hr (hour) or longer and the upper limit is, for example, For example, not less than 40 hr and not more than 30 hr, and the range is, for example, not less than 1 hr and not more than 50 hr, for example, not less than 3 hr and not more than 40 hr, For more than 4 hrs, it is less than 30 hrs.

As described above, the method for producing a laminated optical film of the present invention can be carried out. The laminated optical film produced by the production method of the present invention can be, for example, a roll-shaped porous article, and has advantages such as good manufacturing efficiency and easy handling.

The laminated optical film (void layer) of the present invention thus obtained may be laminated with another film (layer), for example, to form a laminated structure including the porous structure. In this case, in the laminated structure, the respective components may be laminated via, for example, a pressure-sensitive adhesive or an adhesive.

[2.4 Details of Manufacturing Method of Laminated Optical Film Using Long Film]

The lamination of the respective components may be laminated by continuous processing using a long film (so-called Roll to Roll or the like) from the viewpoint of efficiency, for example, Or may be laminated.

Hereinafter, the method of forming the void layer and the cover layer of the present invention on a substrate (resin film) will be described with reference to FIGS. 1 to 3 by way of example. 2 shows a step of winding and coiling a protective film after forming the above-mentioned silicon porous article. However, in the case of laminating another functional film, the above-mentioned technique may be used, or another functional film may be coated, After drying, the silicon porous body subjected to the film formation may be bonded just before winding. The film forming system shown in the drawing is merely an example, and the present invention is not limited thereto.

The above-described substrate may be the above-described resin film in the description of the laminated optical film of the present invention. In this case, the void layer of the present invention can be obtained by forming the void layer on the substrate. The void layer of the present invention can also be obtained by laminating the void layer on the above-mentioned resin film in the description of the void layer of the present invention after forming the void layer on the substrate.

1 schematically shows an example of a process in the production method of the present invention in which the above-described void layer and the above-mentioned cover layer are laminated in this order on the substrate (resin film). 1, the method of forming the void layer includes a coating step (1) of forming a coating film on the base material (resin film) 10 by coating the solution of the fine particle of the fine particles 20 " (For example, crosslinking treatment) is performed on the coating film 20 'by drying the coating liquid 20' 'to form a coating film 20' after drying, (4) for improving the strength of the void layer (20) and forming the void layer (21) with improved strength, a step (4) for improving the strength of the void layer (Cover layer raw material liquid coating process) 5 for directly coating the cover layer raw material liquid 22 "on the substrate 21 and drying the coated cover material raw liquid 22" A drying step (6) for forming a film (22 '), a chemical treatment step (for example, a crosslinking treatment) for forming the cover layer (22) , To increase the strength of the cross-linking step), (7), the cover layer 22, includes the strength the step (8), the strength improved covering layer (23). By the above steps (1) to (8), as shown in the figure, the laminated optical film in which the gap layer 21 and the cover layer 23 are stacked in this order is manufactured on the resin film 10 . The method for producing a laminated optical film of the present invention may or may not suitably include steps other than the above steps (1) to (8). The step (4) of the above step may be performed also as the step (8) of the cover layer. That is, in the step (8) for improving the strength of the cover layer, the strength of the gap layer may be simultaneously improved.

The coating method of the sol particle liquid 20 "in the coating step (1) is not particularly limited and a general coating method may be employed. As the coating method (1), for example, a slot die method, (Dip coating method), spin coating method, brush coating method, roll coating method, flexo printing method, wire bar coating method, spray coating method, extrusion coating method A curtain coating method, a roll coating method, a micro-gravure coating method and the like are preferable from the viewpoints of productivity, flatness of a coating film, etc. Among these, the extrusion coating method, the curtain coating method, the roll coating method and the micro gravure coating method are preferable. The coating amount of the sol particle liquid 20 "is not particularly limited and may be suitably set, for example, so that the thickness of the gap layer 20 becomes appropriate. The thickness of the gap layer 21 is not particularly limited and is, for example, as described above.

(The precursor of the void layer) 20 'after the drying process (2) is performed by drying the sol particle liquid 20' '(that is, removing the dispersion medium contained in the sol particle liquid 20' ). The conditions of the drying treatment are not particularly limited and are as described above.

In the chemical treatment step (3), a coating film (20 ') containing the catalyst added before coating (for example, a photoactive catalyst, a photocatalyst generating agent, a thermally active catalyst or a heat catalyst generating agent) The microporous particles in the coating film 20 'are chemically bonded (for example, crosslinked) to form the microporous layer 20 by light irradiation or heating. The light irradiation or heating conditions in the chemical treatment step (3) are not particularly limited, and are as described above.

Further, in the strength improving step (4), the strength of the gap layer (20) is improved. The treatment temperature and the treatment time in the strength improving step (4) are not particularly limited and are as described above. The present step (4) may be carried out at the same time as the step (8) described later. Alternatively, immediately after the step (3), the cover layer coating step (5) may be carried out. At this time, it may be wound once before the step (5), or the coating step (5) may be carried out continuously without winding.

The method for coating the cover layer raw material liquid 22 "in the coating process (5) is not particularly limited, and the method exemplified in the coating process (1) may be used. ") Is not particularly limited, and can be appropriately set so that the thickness of the cover layer 22 becomes appropriate. The thickness of the cover layer 22 is not particularly limited and is as described above.

In the drying step (6), the conditions of the drying treatment for drying the cover layer raw material liquid 22 "are not particularly limited, and the same drying treatment conditions as in the drying step (2) may be used.

In the chemical treatment step 7, the fine pore particles of the gap layer 21 and the compound in the cover layer raw material solution 22 " are chemically bonded (for example, by crosslinking) ) And a cover layer 22. The light irradiation or heating conditions in the chemical treatment step 7 are not particularly limited and may be the same as in the chemical treatment step (3).

Further, in the strength improving step (8), the strength of the cover layer (22) is improved. The treatment temperature and the treatment time in the strength improving step (8) are not particularly limited, but are, for example, as described above.

Next, Fig. 2 schematically shows an example of a coating apparatus of the slot die method and a method of forming the void layer using the coating apparatus. 2 is a sectional view, but the hatch is omitted for easy viewing.

As shown in the figure, each step in the method using this apparatus is carried out while conveying the base material 10 in one direction by the rollers. The conveying speed is not particularly limited and is, for example, 1 to 100 m / min, 3 to 50 m / min, and 5 to 30 m / min.

First, a coating process (1) is carried out in which the substrate 10 is coated with the sol particle liquid 20 " in the coating roll 102 while feeding the substrate 10 from the delivery roller 101, Subsequently, the process proceeds to the drying step (2) in the oven zone 110. In the coating device of Fig. 2, a preliminary drying step is carried out after the coating step (1) and before the drying step (2) In the drying step (2), the heating means (111) is used. As described above, the heating means (111) may be a hot air fan, a heating roll, A far-infrared heater, or the like can be suitably used. Further, for example, the drying step (2) may be divided into a plurality of steps, and the drying temperature may be increased as the subsequent drying step is performed.

After the drying step (2), the chemical treatment step (3) is carried out in the chemical treatment zone (120). In the chemical treatment step (3), for example, when the coated film 20 'after drying includes a photoactive catalyst, light is irradiated to the lamp (light irradiation means) 121 disposed above and below the substrate 10, Investigate. Alternatively, for example, when the coated film 20 'after drying includes a thermally active catalyst, the film is irradiated on the upper side and the lower side of the substrate 10 using a hot air (heating means) instead of the lamp (light irradiation device) And the base material 10 is heated by the disposed hot air 121. By this cross-linking treatment, the microporous particles in the coating film 20 'are chemically bonded to each other, and the gap layer 20 is cured and strengthened. In this example, the chemical treatment step (3) is carried out after the drying step (2). However, as described above, it is preferable that at any stage of the production method of the present invention, It is not limited. For example, as described above, the drying step (2) may also serve as the chemical treatment step (3). Further, even in the case of chemical bonding occurring in the drying step (2), the chemical bonding step (3) may be further performed to further strengthen the chemical bonding between the fine pore particles. Further, in the pre-drying step (for example, the preliminary drying step, the coating step (1), the step of producing the coating liquid (suspension, etc.)), the chemical bonding between the pulverized products I can get up.

After the chemical treatment step (3), the strength improving step (4) is carried out in the strength improving zone (130). In the strength improving step 4, the gap layer 20 may be heated, for example, by using a hot air (heating means) 131 disposed on the base material 10. The heating temperature, time and the like are not particularly limited, but are, for example, as described above.

After the strength improving step (4), the coating step (5) is carried out in the cover layer coating zone (140). In the coating step (5), for example, the cover layer raw material solution is directly applied (coated) onto the gap layer 20 by the cover layer coating means 141. [ Further, as described above, instead of applying (coating) the cover layer raw material liquid, a tape or the like having a cover layer may be bonded (pasted).

After the coating step (5), the drying step (6) is carried out in the oven zone (150) using the heating means (151). Prior to the drying step (6), a preliminary drying step may be carried out at room temperature or the like, and the drying step (6) may be divided into a plurality of steps, and the drying temperature may be increased as the subsequent drying step is performed. As the heating means 151, the illustrated heating means 111 may be used in the drying step (2).

After the drying step (6), the chemical treatment step (7) is carried out in the chemical treatment zone (160) using the light irradiation means or the heating means (161). In the chemical treatment step (7), for example, the compound in the cover layer and the microporous particles in the void layer are cross-linked by chemical bonding.

After the chemical treatment step (7), the strength improving step (8) is carried out by the heating means (171) in the strength improving zone (170). The heating temperature and the treatment time in the strength improving step (8) are as described above.

(5), the drying step (6), and the chemical treatment step (7) are carried out prior to the strength improving step (aging step) (4) in the formation of the void layer and the cover layer The strength of the cover layer is improved by the heating means 171 and the gap layer is also heated by the heating means 171 when the strength increasing step (aging step) A strength improving step (aging step) 4 may be performed. As a result, for example, the compound in the cover layer and the microporous particles of the gap layer can be gelled at the same time, so that the adhesion between the cover layer and the gap layer is improved, and the scratch resistance of the cover layer is also improved .

Then, after the strength improving step (8), the laminate is wound by the winding roll 105. Further, for example, the laminate may be covered with a protective sheet fed from the roll 106, or may be covered with another layer formed from a long film instead of the protective sheet.

Fig. 3 schematically shows an example of a coating apparatus of the micro gravure method (micro gravure coating method) and a method of forming the void layer using the same. The figure is a sectional view, but the hatch is omitted for easy viewing.

As shown in the figure, each step in the method using this apparatus is carried out while conveying the base material 10 in one direction with the rollers in the same manner as in Fig. The conveying speed is not particularly limited and is, for example, 1 to 100 m / min, 3 to 50 m / min, and 5 to 30 m / min.

First, a coating step (1) for coating a sol liquid 20 "on the base material 10 while conveying the base material 10 from the delivery roller 201 is carried out. As shown in the drawing, coating is performed using a liquid reservoir 202, a doctor (doctor knife) 203, and a micro gravure 204. More specifically, while the sol liquid 20 "stored in the liquid reservoir 202 is attached to the surface of the micro gravure 204 and controlled to a predetermined thickness by the doctor 203, the micro gravure 204 ) Is applied to the surface of the base material 10. The micro gravure 204 is an example, and the present invention is not limited to this, and any other coating means may be used.

Next, the drying step (2) is carried out. Specifically, as shown in the figure, the base material 10 coated with the sol particle liquid 20 " is transported in the oven zone 210, and heated by the heating means 211 in the oven zone 210, The particle liquid 20 "is dried. The heating means 211 may be the same as, for example, Fig. Also, for example, by dividing the oven zone 210 into a plurality of sections, the drying step (2) may be divided into a plurality of steps, and the drying temperature may be increased as the subsequent drying step is performed. After the drying step (2), the chemical treatment step (3) is carried out in the chemical treatment zone (220). In the chemical treatment step (3), for example, when the dried coating film 20 'includes a photoactive catalyst, the lamp (light irradiation means) 221 disposed above and below the base material 10 Investigate. Alternatively, for example, when the coated film 20 'after the drying includes a thermally active catalyst, it is possible to use a hot air heater (heating means) in place of the lamp (light irradiating device) And the base material 10 is heated by the disposed hot air (heating means) 221. By this cross-linking treatment, the ground particles in the coating film 20 'are chemically bonded to each other to form the gap layer 20.

After the chemical treatment step (3), the strength improving step (4) is carried out in the strength improving zone (230). In the strength improving step 4, for example, the air gap layer 20 may be heated by using hot air (heating means) 231 arranged above and below the base material 10. The heating temperature, time and the like are not particularly limited, but are, for example, as described above.

After the strength improving step (4), the coating step (5) is carried out in the cover layer coating zone (240). In the coating step (5), for example, the cover layer raw material solution is directly applied (coated) on the gap layer 20 by the cover layer coating means 241. [ Further, as described above, instead of applying (coating) the cover layer raw material liquid, a tape or the like having a cover layer may be bonded (pasted).

After the coating step (5), the drying step (6) is carried out in the oven zone (250) using the heating means (251). Prior to the drying step (6), a preliminary drying step may be carried out at room temperature or the like, and the drying step (6) may be divided into a plurality of steps, and the drying temperature may be increased as the subsequent drying step is performed. As the heating means 251, the illustrated heating means 211 may be used in the drying step (2).

After the drying step (6), the chemical treatment step (7) is carried out in the chemical treatment zone (260) using a light irradiation means or a heating means (261). In the chemical treatment step (7), for example, the compound in the cover layer and the microporous particles in the void layer are cross-linked by chemical bonding.

After the chemical treatment step (7), the strength improving step (8) is performed in the strength improving zone (270). The heating temperature and the treatment time in the strength improving step (8) are as described above.

[3. Optical member]

The optical member of the present invention is characterized by including the laminated optical film of the present invention as described above. The optical member of the present invention is characterized by including the laminated optical film of the present invention, and the other structures are not limited at all. The optical member of the present invention may further include another layer in addition to the above-described laminated optical film of the present invention, for example.

Further, the optical member of the present invention includes, for example, the laminated optical film of the present invention as a low reflection layer. The optical member of the present invention may further include another layer in addition to the above-described laminated optical film of the present invention, for example. The optical member of the present invention is, for example, in the form of a roll.

[4. Image display device]

The image display apparatus of the present invention is characterized by including the optical member of the present invention as described above. The image display apparatus of the present invention is characterized by including the optical member of the present invention, and the other configurations are not limited at all. The image display apparatus of the present invention may further include other structures besides the above-described optical member of the present invention, for example.

Example

Next, an embodiment of the present invention will be described. However, the present invention is not limited to the following examples.

(Example)

In this embodiment, the laminated optical film of the present invention was produced as follows. The number of the substances used in the production is, unless otherwise stated, parts by weight (parts by weight). The concentration (%) is, unless otherwise stated,% by weight.

[Reference Example 1: Formation of Blank Layer]

To 18 parts of DMSO, 8 parts of methyltrimethoxysilane was dissolved. To the mixed solution, 4 parts of an oxalic acid aqueous solution of 0.01 mol / l was added, and the mixture was stirred at room temperature for 30 minutes to hydrolyze methyltrimethoxysilane. 65 parts of DMSO, 3 parts of ammonia water at a concentration of 28% and 2 parts of pure water were added, followed by agitation at room temperature for 15 minutes and heating at 40 占 폚 for 20 hours to obtain a gel-like compound. The gel compound was crushed into granules of several millimeters to several centimeters in size, IPA was added in an amount of 4 times the amount of the gel, and the mixture was gently stirred and then allowed to stand at room temperature for 6 hours to decant the solvent and the catalyst in the gel . The same decantation treatment was repeated three times to complete the solvent substitution. The gel-like compound was subjected to high-pressure medialess milling (Homogenizer (trade name UH-50, manufactured by SMT Co.)) to prepare a sol solution. The volume average particle diameter indicating the particle size deviation of the sol solution at this time was found to be 0.50 to 0.70 as determined by a dynamic light scattering type nano-track particle size analyzer (trade name: UPA-EX150, manufactured by Nikkiso Co., Ltd.). Further, IPA (isopropyl alcohol) solution of 1.5 wt% of a photogenerating catalyst (Wako Pure Chemical Industries, Ltd .: trade name WPBG266) was prepared, and 0.031 part was added to 0.75 part of the sol liquid to prepare a 5% Ethoxysilyl) ethane was added to prepare a coating solution. The coating solution was applied to the surface of a polyethylene terephthalate substrate (resin film) to form a coating film. The coating film was treated at a temperature of 100 DEG C for 1 minute and dried to form a silicon porous film having a thickness of 1 mu m. Thereafter, the porous film was subjected to UV irradiation (350 mJ / cm < 2 > (@ 360 nm)) and further heating aging at 60 DEG C for 20 hours to obtain an air gap layer.

[Reference Example 2: Formation of a gap layer]

Alumina sol solution (4.9% concentration: Kawa Ken Fine Chemical Co., Ltd.) in 20 parts, were added 13 parts of water, and then heated at 80 ℃, was added 3 parts of NH _3. And further heated at 80 DEG C for 10 hours to obtain a gel-like compound. The same operation as in Reference Example 1 was carried out except that this gel-like compound was used in place of the gel-like compound in Reference Example 1 to obtain a low refractive index porous layer having a refractive index of 1.24.

[Reference Example 3: Formation of cavity layer]

After dissolving n-hexadecyltrimethylammonium chloride and urea in a cellulose nanofiber sol solution (2% concentration: manufactured by Suginomachine), MTMS was added to hydrolyze. Thereafter, the mixture was heated at 60 DEG C for 20 hours to obtain a gel-like compound. The same operation as in Reference Example 1 was carried out except that this gel-like compound was used in place of the gel-like compound in Reference Example 1 to obtain a low refractive index porous layer having a refractive index of 1.20.

[Reference Example 4: Formation of Blank Layer]

The same operation as in Reference Example 1 was carried out except that the gel compound of Reference Example 1 was changed to a dispersion of needle-shaped silica gel IPA-ST-UP (trade name of Nissan Chemical Industries Co., Ltd.) to obtain a low refractive index void layer having a refractive index of 1.19 .

[Example 1]

A cover prepared by blending 40 parts of polyvinyl alcohol (trade name: JC40: polymerization degree 4000) (9% aqueous solution), 60 parts of methyltrimethoxysilane, 15 parts of urea and 4 parts of BYK333 (trade name) Layer composition aqueous solution (cover layer raw material solution) was coated and dried by heating at 100 DEG C for 4 minutes. Further, aging was carried out at 60 DEG C for 20 hours to obtain a laminated optical film. This laminated optical film was a laminated optical film in which the void layer was formed on the polyethylene terephthalate base material (resin film) and a cover layer having a film thickness of 1 mu m was directly formed on the void layer. Table 1 shows the evaluation results of this laminated optical film.

[Example 2]

A laminated optical film was obtained in the same manner as in Example 1 except that VC-10 (trade name) having a degree of polymerization of 1000 was used instead of JC40 as the polyvinyl alcohol as the raw material liquid for the cover layer. Table 1 shows the evaluation results of this laminated optical film.

[Example 3]

A laminated optical film was obtained in the same manner as in Example 1 except that the composition of polyvinyl alcohol and methyltrimethoxysilane in the raw material liquid for the cover layer was changed to 30 parts of polyvinyl alcohol and 70 parts of methyltrimethoxysilane. Table 1 shows the evaluation results of this laminated optical film.

[Example 4]

A laminated optical film was obtained in the same manner as in Example 1 except that the composition of polyvinyl alcohol and methyltrimethoxysilane in the raw material liquid for the cover layer was changed to 70 parts of polyvinyl alcohol and 30 parts of methyltrimethoxysilane. Table 1 shows the evaluation results of this laminated optical film.

[Example 5]

A laminated optical film was obtained in the same manner as in Example 1 except that urea in the raw material liquid for the cover layer was changed to 7 parts of? -Picolin. Table 1 shows the evaluation results of this laminated optical film.

[Example 6]

The composition of the cover layer raw material liquid was changed to 95 parts of a polyester polyol urethane-based polymer (17.5% aqueous solution) (trade name x-7096; manufactured by Nikka Chemical), 5 parts of methyltrimethoxysilane, 3 parts of urea and 4 parts of BYK3500 The procedure of Example 1 was otherwise repeated to obtain a laminated optical film. Table 1 shows the evaluation results of this laminated optical film.

[Example 7]

A laminated optical film was obtained in the same manner as in Example 1 except that the cover layer raw material liquid was changed to a cation-type self-crosslinking nanoemulsion (trade name: UW-550CS: Daisepine Chemical). Table 1 shows the evaluation results of this laminated optical film.

[Example 8]

A laminated optical film was obtained in the same manner as in Example 1 except that urea in the raw material liquid for the cover layer was changed to 7 parts of? -Picolin. Table 1 shows the evaluation results of this laminated optical film.

[Example 9]

A laminated optical film was obtained in the same manner as in Example 1 except that the void layer obtained in Reference Example 2 was used in place of the void layer obtained in Reference Example 1. Table 1 shows the evaluation results of this laminated optical film.

[Example 10]

A laminated optical film was obtained in the same manner as in Example 1 except that the void layer obtained in Reference Example 3 was used in place of the void layer obtained in Reference Example 1. Table 1 shows the evaluation results of this laminated optical film.

[Example 11]

A laminated optical film was obtained in the same manner as in Example 1 except that the void layer obtained in Reference Example 4 was used in place of the void layer obtained in Reference Example 1. Table 1 shows the evaluation results of this laminated optical film.

[Comparative Example 1]

Evaluation was carried out without forming a cover layer on the void layer obtained in Reference Example 1 as it is. The evaluation results are shown in Table 1.

[Comparative Example 2]

Evaluation was carried out without forming a cover layer on the void layer obtained in Reference Example 2 as it is. The evaluation results are shown in Table 1.

[Comparative Example 3]

Evaluation was carried out without forming a cover layer on the void layer obtained in Reference Example 4 as it is. The evaluation results are shown in Table 1.

[Comparative Example 4]

A composition liquid prepared by blending 100 parts of a cyclohexane solution (40% solution) of methyltrimethoxysilane and 10 parts of a Ti catalyst (trade name: TA-25: Matsumoto Fine Chemicals) was applied to the void layer obtained in Reference Example 1, min for heating and drying to form a cover layer to obtain a laminated optical film. The laminated optical film was a laminated optical film in which the void layer was formed on the polyethylene terephthalate base material (resin film), and a cover layer having a film thickness of 1 mu m was directly formed on the void layer. Table 1 shows the evaluation results of this laminated optical film.

[Comparative Example 5]

80 parts of an alicyclic epoxy monomer (trade name: Celloxide: manufactured by Daicel Chemical Industries, Ltd.), 20 parts of an oxetane monomer (trade name: OXT-221: TOA synthesis) and 20 parts of a photocathion initiator (trade name CP- Manufactured by SANA PROPHYLENE CO., LTD.) Was coated and irradiated with UV 1000 mJ to form a cover layer to obtain a laminated optical film. This laminated optical film was a laminated optical film in which the void layer was formed on the polyethylene terephthalate base material (resin film) and a cover layer having a film thickness of 1 mu m was directly formed on the void layer. Table 1 shows the evaluation results of this laminated optical film. In Table 1, " scratch resistance " is the scratch resistance of the cover layer. Quot; refractive index " and " porosity " are the refractive index and porosity of the void layer, respectively. The " contact angle " is the contact angle of water in the gap layer. The porosity of the void layer and the contact angle of water were measured by the method described above. The refractive index of the void layer and the scratch resistance of the cover layer were measured by the following evaluation method (measurement method).

(Assessment Methods)

[Refractive index]

After forming the void layer (void layer of the present invention) on the acrylic film, it was cut into a size of 50 mm x 50 mm, and this was adhered to the surface of a glass plate (thickness: 3 mm) as an adhesive layer. The center portion of the rear surface of the glass plate (about 20 mm in diameter) was painted with black magic to prepare a sample that did not reflect on the back surface of the glass plate. The sample was set in an ellipsometer (manufactured by J. A. Woollam Japan, trade name: VASE), and the refractive index was measured under the conditions of a wavelength of 500 nm and an incident angle of 50 to 80 degrees.

[Scratch resistance]

Steel wool test (? 25 mm) 100 g load × 10 reciprocations were carried out to visually confirm the presence or absence of scratches.

As shown in Table 1, according to this example, a laminated optical film capable of achieving both high porosity (porosity) and excellent scratch resistance was obtained. In Examples 1 to 11, the porosity of the cover layer was measured by the same measurement method as the porosity of the void layer, and as a result, it was 10 vol% or less in all cases.

Industrial availability

As described above, the laminated optical film of the present invention can achieve both a high porosity (porosity) and excellent scratch resistance. Further, according to the method for producing a laminated optical film of the present invention, it is possible to produce the laminated optical film of the present invention having both high porosity (porosity) and excellent scratch resistance. The laminated optical film of the present invention can be used, for example, in the optical member and the image display apparatus of the present invention, but the present invention is not limited thereto and may be used for any purpose.

10; materials
20; Cavity layer
20 '; Coating film (after drying)
20 ": a sol particle liquid
21; Enhanced cavity layer
22; Cover layer
22 '; Coating film (after drying)
22 "; the cover layer raw material liquid
23; Strengthened cover layer
101; Delivery roller
102; Pot roll
105; Winding roll
106; role
110; Oven zone
111; Heat air (heating means)
120; Chemical treatment zone
121; Lamp (light irradiation means) or hot air (heating means)
130; Strength improvement zone
131; Heat air (heating means)
140; Cover layer coating zone
141; Cover layer coating means
150; Oven zone
151; Heating means
160; Chemical treatment zone
161; Heating means
170; Strength improvement zone
171; Heating means
201; Delivery roller
202; Liquid reservoir
203; Doctor (Doctor Knife)
204; Micro gravure
210; Oven zone
211; Heat air (heating means)
220; Chemical treatment zone
221; Lamp (light irradiation means) or hot air (heating means)
230; Strength improvement zone
231; Heat air (heating means)
240; Cover layer coating zone
241; Cover layer coating means
250; Oven zone
251; Heating means
260; Chemical treatment zone
261; Heating means
270; Strength improvement zone
271; Heating means
351; Winding roll

Claims (14)

A void layer is formed on the resin film,
Further, a cover layer is formed directly on the void layer,
Wherein the gap layer has a water contact angle of 90 DEG or more and a porosity of 30% by volume or more. The method according to claim 1,
And the porosity of the cover layer is not more than 10% by volume. 3. The method according to claim 1 or 2,
Wherein the cover layer is a layer having scratch resistance. 4. The method according to any one of claims 1 to 3,
Wherein the cover layer comprises at least one of a water soluble crosslinking agent and a water-soluble polymer. 5. The method according to any one of claims 1 to 4,
And the refractive index of the gap layer is 1.3 or less. 6. The method according to any one of claims 1 to 5,
The void layer includes a portion directly or indirectly chemically bonded to one or a plurality of kinds of constituent units forming a fine void structure,
Wherein the void layer comprises a crosslinking aid for indirectly bonding the constituent units. The method according to claim 6,
Wherein the content of the crosslinking aid in the void layer is 0.01 to 20% by weight based on the weight of the constituent unit. A method for producing a laminated optical film according to any one of claims 1 to 7,
A void layer forming step of forming the void layer on the resin film, and
And the cover layer forming step of forming the cover layer directly or by transfer on the void layer. 9. The method of claim 8,
Wherein in the cover layer forming step, the cover layer is formed by coating of an aqueous paint. 10. The method according to claim 8 or 9,
In the cover layer forming step, the cover layer raw material liquid containing the raw material for the cover layer is directly applied onto the void layer to form a coating film on the coating layer or another substrate, and transferred onto the void layer. And the cover layer is formed by performing at least one of the steps. 11. The method according to any one of claims 8 to 10,
Wherein the void layer is formed by indirectly bonding one or plural kinds of constituent units forming a fine void structure with the aid of a crosslinking aid in the void layer forming step. 12. The method of claim 11,
Wherein the addition amount of the crosslinking aid is 0.01 to 20% by weight based on the weight of the structural unit. An optical member comprising the laminated optical film according to any one of claims 1 to 7. An image display device comprising the optical member according to claim 13.

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